Forumdude808
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Phase Transfer Oxidation of Piperic Acid
Phase Transfer Oxidation Of Piperic Acid
"In a 250 ml two- or three-necked round bottomed flask, place 1.0g of piperic acid, .1 g of Adogen 464, 10-15 ml of benzene, and
a magnetic stirring bar. Attach a thermometer to the flask through a cork or adapter as well as a smalldropping funnel. Add to this stirred mixture
4.4g of potassium permanganate
dissolved in 50-60 ml of water at such a rate that the reaction temperature remains below 30 degrees. After all of the potassium permanganate has been
added, stir at room temperature for 90 minutes. Finally, add about 10-20 ml ofsaturate sodium bisulfite solution to the reaction mixture and collect
the preciptated manganese dioxide by suction filtration. Wash the precipitate with
10 ml of benzene. Place the filtrate in a separatory funnel,separate the layers, and wash the benzene layer three times with 10ml of 10% NaOH
solution. Wash the base solution once with 20ml of ether. Carefully acidify the base solution to pH 1-2 with 6M HcL and extract the acid solution with
3x25ml ether.
Dry the ether solution over magnesium sulfate, filter, and then remove the etherby use of a rotary evaporator. The yield was approx. .3 grams
piperonylic acid."Obviously, some sort of scale up is necessary to get an amount of product for a
workable synth.
Is this a viable route ? Im a chem engineering student (first year)
Would you be able to swap out the benzene for like toluene.Is there anything i could use instead of Methyltrialkyl(C8C10)ammonium chloride? I need to
get from piperine to piperonal for a lab...
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Crowfjord
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If you need piperonal, you might want a different method. The product given for the procedure you posted is piperonylic acid
(1,3-benzodioxol-5-carboxylic acid).
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Metacelsus
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And what do you plan to use the product for, exactly? I can't imagine that a school lab assignment would have you make piperonal.
[Edited on 9-10-2014 by Cheddite Cheese]
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Magpie
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You must be an advanced student to be doing this synthesis - normally chemE students don't take organic lab until their 2nd year. And such a
sophisticated synthesis so early in the school year? 
Pray what school are you attending?
The single most important condition for a successful synthesis is good mixing - Nicodem
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Chemosynthesis
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I only one chemical engineer who did this kind of advanced chemistry (for an engineer). He had a PhD and was working research and teaching. It's very
rare for even a chemistry student to make their own lab procedure....
How about just coming clean and not treating us like idiots?
[Edited on 10-10-2014 by Chemosynthesis]
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zed
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Normally? When I was in school, I was allowed to do pretty much whatever I wanted to.
Independent studies they called it. Chem 49. Design your own projects. Get credit.
Not many rules. Make it something interesting. Don't get killed. Obtain authorization for experiments. Don't make anything terribly dangerous or
illegal.
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Amos
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Such a warm welcome everyone is giving this person. You know, I'd really like to make some piperonal too. To make drugs? No, because it supposedly
smells wonderful. Give them a chance, it's not like they used kewl-ish language or asked to be spoon-fed anything, or like they've requested how to
make pseudoephedrine.
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Chemosynthesis
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| Quote: | | [quote&author=No Tears Only Dreams Now]Such a warm welcome everyone is giving this person. |
Actually, it's exactly as though they asked to make pseudoephedrine according to the DEA Chemical Handler Handbook and the amended Controlled
Substances Act and the United Nations International Control Board.
I got to make some of my labs too, back in undergrad. Not as a first year student, not without inventory/stockroom, and safety approval, and assuming
the OP is even being honest, this isn't explicitly a schoolwork site (beginner's is more suited to that). The OP should cite his reference per forum
rules, and I would be extremely sceptical of a first year engineering student making an organic chemistry lab to produce a list 1 chemical. In
addition, they made what seems like a mistake (acid to aldehyde?).
If I'm wrong about them, they can set me straight. I just know how annoying it is to fill out scheduled narcotics paperwork for science, and yef still
have to comply.
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Forumdude808
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I was like half asleep when I posted that, wrong writeup... sorry
But my deal is that Ive been accepted into the honours program and I'm 17! Im going to the University of Alberta, they fail half of their first year
students..... I've finished all my labs for the entire semester by hanging out in the lab day and night so I have some spare time on my hands and Ive
become great mates with my lab instructor so he's letting me do some more advanced 2nd year labs ahead of time. I'm extremely interested in organic
chemistry and food chemistry and Hybrid nano structured materials. Im in love with aromatics as well . Im not sure if I'm actually going to be allowed
to do the piperine to piperonal procedure but I need the Pre lab write up to present to him before he actually gives me a yes or no answer btw
piperonal is supposed to smell like warm marshmellowy , vanilla , cherry. For the ones who think I'm going to go out and make a drug from piperonal,
If I'm even granted access to follow through with this lab , the quantites of piperonal Ill be making will be on the mg scale.
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Forumdude808
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This is a rough draft of my lab procedure, tell me what you guys think...
Piperdine Extraction
Place 15g of ground black pepper in a 500ml RBF add 150ml of 95% Ethanol (EtOH) add boiling chips and heat a reflux for 2 hours
Filter the mixture , throw out black pepper mush and then concentrate the filtrate down to around 10-15ml by simple distillation
Add the concentrated pepper extract to 10ml of a 10% of NaOH solution in 95% EtOH
Heat the solution and add water drop wise ( A yellow precipitate will form ) keep adding water until no more solids appear to form and then allow the
mixture to stand for 24 hours
collect the solid through filtration
Recrystalize
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Chemosynthesis
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Is there a reason you are reducing the procedure time from the Erowid reproduction other than convenience/laziness/failed plagiarism avoidance?Is
there a reason you have avoided citing your source twice now rather than just being upfront?
http://www.erowid.org/archive/rhodium/chemistry/3base/pipero...
I really wouldn't run this past your professor without citing it, and understanding what functional groups are in play here.
You also seemingly aren't reading either our replies or the title headings as to what your products would be. That alone makes me question your whole
advanced schooling spiel. I am sure the members here know piperonal is used in scents, but "BTW" you admitted to wanting to make it into a list
1/class A precursor recognized as such by your country. How about you play with some esters? Simple chemistry, plenty of them smell nice and aren't
pharmacophores, shorter reaction times without the hassles of purification.
Edit: and I highly doubt your stockroom or professors would be able to let you finish your labs day and night. The liabilities and logistics don't add
up. Nothing you have said so far makes any sense to me.
The people on this forum aren't idiots. Go look at what a class A precursors is in Canada and then ask a professor if you can make one. They will tell
you no. That should kill the thread if it were legitimate. If you are so chummy with your professor, why not have them answer such questions? All us
spoonfeeding you will do is make it incrementally more likely to bring further bureaucracy and restrictions over hobby chemistry and professional
science alike, while rewarding poor posting/reading comprehension, and not encouraging you to learn.
[Edited on 10-10-2014 by Chemosynthesis]
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lullu
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| Quote: |
2.4. Piperonal from pepper
2.4.1. Oxidative cleavage of piperine by ozonolysis
A stream of ozone gas, generated by a HAILEA HLO-100 Ozone Steriliser
(100 mg of ozone per hour), was passed through a solution of piperine (1.00 g,
3.51 mmol) in a 5% solution of water in acetone. After 8 h, the ozone generator was
switched off and the solution extracted with two 10 mL portions of diethyl ether.
The combined ether extracts were dried over anhydrous sodium sulphate and the
solvent evaporated in vacuo yielding bright yellow oil. Yield: 508 mg (97%).
1
H
NMR: see Fig. S13. GC–MS: see Fig. 2.
2.4.2. Oxidative cleavage of piperine with aqueous KMnO4in THF
An aqueous solution of KMnO4(2.00 g, 12.6 mmol in 40 mL of water) was added
dropwise over a period of 4 h to a solution of piperine (1.00 g, 3.51 mmol in 40 mL of
THF) at 60 8C. After the solution had been added, the mixture was stirred for 4 h
before the MnO2precipitate that had formed was filtered off leaving a pale yellow
solution. The sample was extracted with diethyl ether and the combined extracts
were dried over anhydrous sodium sulphate. The ether was evaporated in vacuo to
yield a dark yellow-orange oil that solidified on cooling. Yield: 340 mg (65%).
1
H
NMR: see Fig. S14. GC–MS: see Fig. 2
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ref:
Synthesis and impurity profiling of MDMA prepared from commonly available
starting materials
Ryan Gallagher, Ronald Shimmon, Andrew M. McDonagh*
Centre for Forensic Science, University of Technology Sydney, Sydney, NSW 2007, Australia
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Magpie
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That little one-legged polywog sure gets a lot of attention on this forum! 
The single most important condition for a successful synthesis is good mixing - Nicodem
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Nicodem
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Not studying sciences is no excuse for ignoring the fact that this forum is about science and therefore citing a procedure without providing a
reference is not an acceptable behaviour here.
…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being
unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their
scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)
Read the The ScienceMadness Guidelines!
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Mush
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Quote: Originally posted by lullu  |
| Quote: |
2.4. Piperonal from pepper
2.4.1. Oxidative cleavage of piperine by ozonolysis
A stream of ozone gas, generated by a HAILEA HLO-100 Ozone Steriliser
(100 mg of ozone per hour), was passed through a solution of piperine (1.00 g,
3.51 mmol) in a 5% solution of water in acetone. After 8 h, the ozone generator was
switched off and the solution extracted with two 10 mL portions of diethyl ether.
The combined ether extracts were dried over anhydrous sodium sulphate and the
solvent evaporated in vacuo yielding bright yellow oil. Yield: 508 mg (97%).
1
H
NMR: see Fig. S13. GC–MS: see Fig. 2.
2.4.2. Oxidative cleavage of piperine with aqueous KMnO4in THF
An aqueous solution of KMnO4(2.00 g, 12.6 mmol in 40 mL of water) was added
dropwise over a period of 4 h to a solution of piperine (1.00 g, 3.51 mmol in 40 mL of
THF) at 60 8C. After the solution had been added, the mixture was stirred for 4 h
before the MnO2precipitate that had formed was filtered off leaving a pale yellow
solution. The sample was extracted with diethyl ether and the combined extracts
were dried over anhydrous sodium sulphate. The ether was evaporated in vacuo to
yield a dark yellow-orange oil that solidified on cooling. Yield: 340 mg (65%).
1
H
NMR: see Fig. S14. GC–MS: see Fig. 2
|
ref:
Synthesis and impurity profiling of MDMA prepared from commonly available
starting materials
Ryan Gallagher, Ronald Shimmon, Andrew M. McDonagh*
Centre for Forensic Science, University of Technology Sydney, Sydney, NSW 2007, Australia |
Synthesis and impurity profiling of MDMA prepared from commonly available starting materials
Forensic Science International
Volume 223, Issues 1–3, Pages e1-e64, 1-376 (30 November 2012)
Pages 306-313
Ryan Gallagher, Ronald Shimmon, Andrew M. McDonagh
Attachment: Piperonal (1MB)
This file has been downloaded 879 times
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AvBaeyer
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If you want piperonal, small quantities are easily available from several perfumery chemical suppliers. It is often listed under some sort of trade
name so you have to look to find it.
AvB
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zed
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Ummm. Piperonal.... Yeah, the brain really loves the smell. It's wonderful.
Why still the big deal? Since the legal restriction of Nitro-ethane sales, Piperonal should be considered a less desirable reagent.
That being said. Benzaldehyde may be steam-distilled from Cinnamaldehyde via a reverse Aldol type procedure. Some reason that this couldn't work for
Piperonal?
Yeah, I know we are talking apples and oranges. But.
[Edited on 11-10-2014 by zed]
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Chemosynthesis
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| Quote: | | Why still the big deal? Since the legal restriction of Nitro-ethane sales, Piperonal should be considered a less desirable reagent
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There are well known analogues that do not require nitroethane as they do not utilize a Henry reaction, but another synthetic route. Plus, there is no
way some ChemE. student had time to spend day and night in his chemistry lab, and on top of that, that his professor could allow him to do so, or that
the stockroom would make special reagent batches for him on the spot and then duplicate their efforts in larger batches for other students. None of
that remotely makes any sense.
Edit: I would prefer someone ask about the Erowid link upfront so we could tell them to learn their functional groups. With an organic text, a little
reading should show how to go from A to B. Obfuscating your source material and then conveniently posting the "wrong" section, and then plagiarizing a
second section of the same source is intellectually dishonest. Same with making up a ridiculous back story about living in the labs as an undergrad
and performing next year's costly experiments before many schools have midterms. Yeah, I have a problem with that. Maybe it's just me.
[Edited on 11-10-2014 by Chemosynthesis]
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zed
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No reason to go all "Sauron" on this fella. Heliotropine is nice. It isn't like he asked us for our secret recipe for Etonitazine.
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Chemosynthesis
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I'm not sure why you want to compare me with Sauron, a fairly controversial member, only after I answered your question about precursor potential, but
other than that I understand your sentiment, and I also understand that even illicit chemistry can incite people into productive legitimate careers,
or hobby chemistry. That said, there is a huge difference between Sauron and myself; Whereas Sauron would be acerbic, I am actually pointing out
logical and factual errors with what is obviously a suspicious story. No one has been able to address that. You ever work in a school or for a stock
room? Really think they would do special preps for a student? Really think they would let an undergraduate student, a first year minor no less,
perform lab assignments day and night? How could that be supervised? What if there were an accident? That just doesn't happen.
I highly doubt Sauron would humor that story by pointing out things such as plagiarism and the legality of the poster's jurisdiction. I also doubt
Sauron would proffer a legal alternative for a school assignment (most simple esters). Any of this should be helpful to an actual student, who should
probably post in Beginnings if they don't understand their functional groups. Functional groups I specified, by the way, so if the OP were so
inclined, could look up in a textbook and learn.
If someone comes in with a story that makes any sense, or can do more than plagiarize Erowid (demonstrating a real effort to comprehend functional
groups), I have no problem with that and I can't prevent someone from learning. I have told questionable posters what chemical concepts they would
need to learn to answer suspect questions before, without giving instructions to directly assist illicit chemistry. If someone just arbitrarily
changes some aspects of an established procedure without explanation, fails to cite sources, and then isn't grasping the differences in their
functional groups, that isn't really putting them in the best light. Combine that with a schedule 1 substance and an impossible explanation?
Last I checked, deference was given to US law because that is where Polverone and the servers are located. I know you can get permission to produce
schedule 1 precursors, but I wouldn't be able to honestly suspend disbelief given the poster's circumstances. And to top it all off, they didn't come
back after they got a route to piperonal. I doubt my suspicion chased them off, as I never directly accused them of anything, but questioned what
didn't make sense. They are still free to come tell me how wrong I am and explain. Do you see anything inappropriate with that?
[Edited on 14-10-2014 by Chemosynthesis]
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zed
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The world won't end if this guy makes a little Piperonal, and I don't care about his cover story. This is just a little exercise in natural products
chemistry.
My concern would be only in the effectiveness of his approach.
Since oxidations are difficult to control, there might be a slight possibility that Piperic Acid can be deconstructed.
It may be synthesized by the action of Acetic Anhydride and Sodium Acetate, on the 3,4-Methylene Dioxy Analog of Cinnamaldehyde. The reaction is
probably driven to completion by Acetic Anhydride sucking up water as it is formed.
The question is.......can this reaction be reversed? Can that formed bond, be rehydrated and broken? Producing the Cinnamaldehyde Analog plus Acetic
Acid.
If so, since we know that Benzaldehyde may be recovered from Cinnamaldehyde via steam distillation from a basic solution....We might assume that
Piperonal might be recovered from steam distillation of the Methylene- Dioxy-Analog.
[Edited on 14-10-2014 by zed]
[Edited on 14-10-2014 by zed]
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Chemosynthesis
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| Quote: | The world won't end if this guy makes a little Piperonal, and I don't care about his cover story. This is just a little exercise in natural products
chemistry.
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I'm not sure whose concerns you're addressing about the world ending, but you can keep that and your Sauron
equating to yourself and keep dealing with whatever inferences you gleaned from the originator's posts, please. Addressing the posts themselves is all
I've done thus far, and addressing synthetic viability at your request.
I chose to address the back story and the legality because I obviously do care, and I am not out of line given the nature of the precursor or the
mistakes of the post, which bring into question the poster's readiness for a chemical discussion. Apparently you don't find anything inappropriate
with my posts, but it seems you don't like them. If that's the case, kindly dislike them in a direct manner in an appropriate thread, or in silence; I
haven't said anything against you or your posts, so show me the same respect.
[Edited on 15-10-2014 by Chemosynthesis]
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